Hydrocarbon compositions containing carbollyl metal complexes

ABSTRACT

THE INVENTION COMPRISES THE USE OF CARBOLLYL METAL COMPLEXES AS ADDITIVES IN HYDROCARBON FUELS AND LUBRICANTS WHERE THEY FUNCTION AS COMBUSTION IMPROVERS, ANTIKNOCK AGENTS AND EXTREME PRESSURE AGENTS. SPECIFIC EMBODIMENTS INCLUDE USE IN FUELS FOR SPARK AND COMPRESSION IGNITION ENGINES, JET ENGINES AND ROCKETS.

D. C. YOUNG HYDROCARBON COMPOSITIONS CONTAINING CARBOLLYL METAL COMPLEXES Filed Dec. '11, 1967 2 Sheets-Sheet 1 INVENTOR.

DOA/4L@ C'. .YOU/VG BY March 2, 1971 D. c. YOUNG 3,567,410

HYDROCARBON COMPOSITIONS CONTAINING CARBOLLYL METAL COMPLEXES Filed Dec. l1, 1967 2 Sheets-Sheet 2 I N VEN TOR. DA/ 0 C. YOU/V6 BY j United States Patent O 3,567,410 HYDROCARBON COMPOSI'IIONS CONTAINING CARBOLLYL METAL COMPLEXES Donald C. Young, Fullerton, Calif., assigner to Union Oil Company of California, Los Angeles, Calif. Filed Dec. 11, 1967, Ser. No. 689,527 Int. Cl. C101 l/28 U.S. Cl. 44--68 9 Claims ABSTRACT OF THE DISCLOSURE The invention comprises the use of carbollyl metal complexes as additives in hydrocarbon fuels and lubricants where they function as combustion improvers, antiknock agents and extreme pressure agents. Specic embodiments include use in fuels for spark and com-pression ignition engines, jet engines and rockets.

DESCRIPTION OF THE INVENTION The invention comprises the combination of a hydrocarbon with a minor but effective amount of a earbollyl metal complex. The metal employed is a metal having orbitals of vr-syrnmetry which in the metallic or ionic state is capable of contributing at least one electron to bonding in the complex. Orbitals of 1r-symmetry are d and p orbitals.

The carbollide is a carbon and boron-containing ligand having the shape of an icosohedron with one missing apex. Its emperical formula is:

X is hydride or halide;

R is alkyl, aryl, alkenyl or haloalkyl;

R is hydride, halide, alkyl, aryl, alkenyl, carboxy, carboxyethyl, cycloalkyl or ammonium;

Y is a ligand which is an unsaturated alicyclic or aliphatic hydrocarbon having from 2 to about 15 carbons or which has at least one atom that is halogen, oxygen, nitrogen, sulfur or trivalent phosphorus, bismuth, arsenic or antimony;

o is 1 or 2;

n is 0, 1 or 2;

p is or l; and

The complexes of the carbollide and metal generally have the following emperical formula:

M is a transition metal with valence, a;

Y is a ligand which is an unsaturated alicyclic or aliphatic hydrocarbon having from 2 to about 15 carbons or which has at least one atom that is halogen, oxygen, nitrogen, sulfur or trivalent phosphorus, bismuth, arsenic or antimony;

R, R', o, m, n and p are as aforementioned;

y is l or 3;

z is l or 2;

q is l or 2;

c=net valence of ligand;

Zia-.valence of carbollyl group; and

xra-i-c-l-b Exceptions to the preceding generalized emperical formula of the complex are the complex dimers and disproportionated dimers. These exist for several of the metals with the carbonyl carbollyl complexes. Examples of these are:

O O B gIIg C QHZMIVII C 0) 5 wherein M and M are Group V--IB metals such as molybdenum or tungsten. Other examples are:

CO CO CO O wherein M and M are Group VIII metals such as iron or cobalt.

The term carbollide as used herein refers to carbon and boron anions having a characteristic shape of a truncated sosahedron, possessing the ability to form cornplexes with metal atoms and corresponding to the following emperical fromulae:

All the preceding are isoelectronic, containing a total of 72 electrons with the net valence, x, dependent on the identity of the X, Y or R groups.

In the preceding formulae:

n is 0, 1 or 2;

b is the. net valence of the ion and is a whole number from -3 to 1;

R is alkyl, aryl, alkenyl or haloalkyl;

R is hydride, halide, alkenyl, alkyl, aryl, carboxyl, carboxylalkyl, cycloalkyl or ammonium;

X is hydride, alkyl or halide;

Y is hydride, halide, aryl, alkenyl, alkyl or cycloalkyl; and

Y is a ligand, i.e., a compound containing an oxygen, nitrogen, sulfur, atom or trivalent, arsenic, antimony, bismuth or phosphorus atom having an unshared pair of electrons available for coordinate covalent or multicenter bonding.

The carbollides have the structure of a regular icosahedron with one vertex missing. The boron and carbon atoms lie in the vertices of the truncated icosahedron and this structure is reflected in the characteristic naming of the anions; the prex clovo indicating a cage structure and the term carbollide being derived from ol1a, the Spanish word for jug which is resembled by the structure of the truncated icosahedral anion.

The carbollides are analogous to cyclopentadienide ion and form /r-complexes with metal atoms in a manner similar to cyclopentadienide ion. The carbollyl metal complexes, however, have greater stability than cyclopentadienyl metal complexes and the carbollyl group also stabilizes the higher oxidation states of the metal. The catalytically active materials useful in this invention are the sandwich bis-1rcarbollyl metal complexes as well as mono-1rcarbollyl metal complexes with one or more additional ligands. As used herein, the term carbollyl metal complex will be generic to the bis-and mono-1r-carbollyl metal complexes.

The figures illustrate the carbollides and their metal complexes as follows:

FIG. 1 illustrates the preparation of various carbollides;

FIG. 2 illustrates the orbitals of the carbollides available for metal complex formation;

FIG. 3 illustrates a B-ligand substituted carbollide;

FIG. 4 illustrates a bis-fr-carbollyl metal complex;

FIG. 5 illustrates a vr cyclopentadienyl 1r carbollyl metal complex;

FIG. 6 illustrates a vr-tricarbonyl-w-carbollyl metal complex; and

FIG. 7 illustrates a vr-tetraphenyl-cyclobutadienylewcarbollyl metal complex. Y

Referring now to FIG. 1, three methods for preparation of carbollide anions are shown. In this diagram, the boron atoms are unshaded and the carbon atoms are shaded. The small shaded spheres represent significant hydrogen atoms While the terminal substituents X, Y, R or R', one of which is attached to each boron or carbon atom, have been omitted from this drawing where these substituents do not significantly affect the preparation of the anions.

The carbollides are prepared from decaborane or alkyl substituted decaborane by either of three preparations which are described in greater detail hereinafter and which are illustrated in the examples.

In preparation A, decaborane is reacted with an acetylene to produce carborane which is degraded with alcoholic base to abstract a boron atom. Treatment of the resultant material with an alkali metal hydride in an anhydrous solvent or treatment with concentrated aqueous base removes the protonic hydrogen which is associated with the open face of the intermediate and thereby forms the dicarbollide anion.

In preparation B, decaborane is reacted with an alkyl or aryl isocyanide which forms a compound having the structure of a truncated icosahedron with an ammonium group on the carbon atom and bridging hydrogen atoms on the two pairs of face boron atoms. Treatment of this compound with strong aqueous base removes the two bridging hydrogens and yields a C-ammonyl monocarbollide anion.

Preparation C reacts an alkali metal cyanide with decaborane to form a divalent cyanoborane anion. This material is passed over an acidic ion exchange solid to close the structure and form a carborate anion which is a homolog of the intermediate of preparation B. This material is then N-alkylated by treatment with a dialkyl sulfate in an alkali metal hydroxide solution. The intermediate of preparation C can similarly be N-alkylated. The fully N-alkylated material can then be treated with an alkali metal hydride in anhydrous solution or with concentrated aqueous alkali metal hydroxide to abstract the trialkyl ammonium group and the two bridging hydrogens from the face of the truncated icosahedron thereby forming a monocarbollide ion. The monocarbollide and dicarbollide anions prepared in methods A, B and C are isoelectronic.

FIG. 2 illustrates the vacant sp3 orbital lobes on the open face of the truncated icosahedron structure of the carbollide anion. Each atom in the anion has a terminal substituent such as X, Y, R or R previously mentioned. The ion is described as the (3)-1,2dicarbollide anion wherein the number in parenthesis refers to the missing boron atom and the 1,2 numbers indicate the positions of the carbon atoms in the icosahedral cage. The corresponding monocarbollide is identified as (3)-1-monocarbollide anion. Isomers of the dicarbollide structure are possible and can be prepared in the manner hereinafter described wherein the carbonatoms occupy other positions in the cage, i.e., the (3)1,7dicarbollide and the (3 -1, IZ-dicarbollide anion.

FIG. 3 illustrates the B-ligand-carbollide structure wherein a ligand such as tetrahydrofuran is substituted on a boron atom. This ligand can be substituted on either of the three boron atoms in the face of the truncated icosahedron and symmetrical and asymmetrical isomers are thereby provided. Two ligand isomers occur with the (3)- 1,2dicarbollide ion. These are symmetric 8ligand-(3) 1,2-dicarbollide and asymmetric 4ligand(3)l,2dicar bollide. Both ligand substituted monocarbollide isomers are asymmetric.

Transition metals are capable of forming 1r molecular orbitals with the ve sp3 orbital lobes shown on the open face of the truncated icosahedron of FIGS. 2 and 3 and these metals will therefore readily complex with the carbollide ions. The metals form a set of three bonding molecular orbitals containing a total of six electrons all of which are provided by the metal atom. When these complexes are formed in the absence of any other ligand, bis-Tr-complexes are formed as are illustrated in FIG. 3 wherein two of the carbollyl truncated icosahedrons are complexed with a single metal atom designated as M. The net valency of this complex is indicated as a-l-b-l-c wherein b is the previously mentioned valence for the carbollide designated as I and c is the valence for carbollide II and a is the formal oxidation state of the metal. This value can be from -6 to -l-2 depending on the value of a, b and c. The more readily prepared complexes have net valencies from -5 to 0, i.e., are neutral or anionic; however, cations can be achieved with strong oxidizing treatments which promote high oxidation states of the metal atom.

In FIG. 4, the metal atom is shown surrounded with a hag molecular orbital. The calculation of this orbital is similar to the Moftt molecular orbital treatment of ferrocene.

The complex can also be formed in the presence of other ligands, i.e., reactants capable of contributing a total of six electrons to form bonding orbitals with a metal atom. FIGS. 5, 6 and 7 illustrate the structure of the catalyst of my invention for the cyclopentadienyl, tricarbonyl and tetraphenyl cyclobutadienyl derivatives, respectively, of the carbollyl metal complex.

CARB OLLIiDE PREPARATION DICARBOLLIDE PREPARATION The dicarbollides used in this invention to prepare dicarbollyl metal complexes are derived from dicarborane (B10H10C2H2) which in turn is derived from decaborane(l4). The preparation is illustrated in FIG. 1, method A. In the preparation of dicarborane, decaborane is puritied by sublimation or recrystallization and dissolved in an organic solvent such as an ether. A Lewis base such as diethyl sulfide, acetonitrile, etc., is added to this solution and the solution is maintained at about 25-85 C. for an extended period while acetylene is passed into contact with the solution. The reaction is as follows:

B1oH14l2(C2H5)2S" B10H12[S(C2H5)2l2 +H2B10H12[S(C2H5)2lz'l-RCECR BioHm (C'R 2l2(C2H5 zSf-Hz The reaction mixture is evaporated under vacuum to remove the Lewis base, e.g., diethyl sulfide, and the solvent. The product is dissolved in an inert solvent and reacted with concentrated hydrochloric acid to convert byproducts to hydrogen and borates. The crude dicarborane is recovered from the solvent by cooling and separating it as a solid. The solid product is washed with aqueous potassium hydroxide, ltered and dried. The dried solid is then extracted with a hydrocarbon solvent and purified dicarborane is crystallized as a solid from the hydrocarbon.

The product from the acetylene addition is 1,2-dicarbaclovododecaborane. Heating of this product neat or in an inert solvent to a temperature of about 500 C. will isomerize the 1,2-dicarborane to the 1,7-dicarborane isomer in substantially total yield. Heating of the 1,7-isomer to about 600 C. will cause further rearrangement to the 1,12-dicarborane.

The dicarborane can be obtained with various substituents on the carbon atoms by the use of appropriately substituted acetylene. Thus bromomethyl dicarborane can be obtained by the use of propargyl bromide rather than acetylene in the aforedescribed preparation. Use of phenyl acetylene likewise provides phenyl dicarborane. In general, any substituted acetylene can be used in the preparation of the dicarboranes and thereby obtain a dicarborane having the same substituent on its carbon atom or atoms. Examples of suitable acetylenic reactants include amyl acetylene, amylmethyl acetylene, butyl acetylene, butylethyl acetylene, butylmethyl acetylene, chloro acetylene, decylmethyl acetylene, di-n-myl acetylene, dibromo acetylene, dibutyl acetylene, diiodo acetylene, diethyl acetylene, dimethyl acetylene, diphenyl acetylene, dipropyl acetylene, divinyl acetylene, ethyl acetylene, ethylpropyl acetylene, n-heptyl acetylene, isopropyl acetylene, methylphenyl acetylene, n-propyl acetylene, vinyl acetylene, etc. These carbon substituted dicarboranes can be thermally isomerized to the 1,7- and 1,12 dicarboranes in the same fashion described in regard to the unsubstituted dicarborane.

The dicarbollide ion can be prepared in two steps from the 1,2- or the 1,7-dicarborane which can have hydrogen or any of the aforementioned substituents on the cage carbon atoms. In the rst step a monovalent dicarbadodecahydroundecaborate anion is obtained by degradation of dicarborane with alcoholic base, e.g., alcoholic solution of potassium hydroxide, sodium hydroxide or piperidine. This is illustrated in FIG. 1 as the second step in method A. In this preparation, the dicarborane is dissolved in a suitable alcohol, e.g., methanol, ethanol, isopropanol, butanol, etc., which contains a strong alkali such as an alkali metal hydroxide or piperidine. The reaction is performed at ambient to reflux temperatures at atmospheric or superatmospheric pressure. The strong base abstracts a boron atom from the carborane which forms a borate ester with the alcohol and evolves hydrogen from the reaction mixture, as follows, with potassium hydroxide in methanol:

After hydrogen ceases to be evolved, the reaction mixture is cooled and the alkali metal dicarbadodecahydroundecaborate can be purified by the precipitation of the excess alkali as the carbonate by saturating the solution with carbon dioxide, filtration, and evaporating the iiltrate to dryness to recover the alkali dicarbadodecahydroundecaborate. 'Ihe resultant salt can be converted to the salt of other cations by base exchange reactions to thereby obtain the ammonium salts or organic ammonium salts.

The monovalent dicarbadodecahydroundecaborate ion can be converted to the divalent dicarbollide anion by treatment to abstract a protonic hydrogen which is associated with the face of the truncated icosahedral dicarbadodecahydroundecaborate ion. This treatment is illustrated in the last step of method A, FIG. 1. The treatment to abtract this protonic hydrogen involves treatment of the dicarbadodecahydroundecaborate ion with an alkali metal, alkali metal hydride or concentrated alkali metal hydroxide. The reaction can be performed in an inert solvent, e.g., tetrahydrofuran, or can be performed with concentrated (at least about 50 weight percent) aqueous alkali metal hydroxide. When the reaction is performed in the inert solvent, the divalent dicarbollide ion or salt thereof can be obtained. The reaction in an aqueous base, however, is performed in the presence of a complex of a transition metal, hereinafter described, and the product is the carbollyl metal complex.

The preparation in an inert solvent is herein described; however, both preparations are illustrated in the examples. Sodium hydride can conveniently be used as a 50 percent dispersion in tetrahydrofuran. The alkali metal salt of the dicarbadodecahydroundecaborate ion is added to the dispersion and the temperature is raised to reflux temperature at which point hydrogen is evolved. The resultant dicarbollide anion precipitates as the alkali metal dicarbollide and can be recovered from the solvent by filtration. The precipitate can be purified by extraction with a hydrocarbon to obtain a residue comprising the puried alkali metal dicarbollide.

The alkali metal salt can be obtained as the salt of other cations by base exchange reactions in non-protonic solvents with such cations, e.g., ammonium chloride, tetramethyl ammonium chloride, other alkali metal salts such as cesium or rubidium chloride, etc. This dicarbollide anion is employed to form dicarbollyl metal complexes which serve as catalysts in my invention.

MONOCARBOLLIDE PREPARATION The monocarbollide anion used in this invention to prepare carbollyl metal complexes. is prepared from an alkylammonium carborane having the general formula wherein R is hydrogen or alkyl and R is alkyl such as methyl, ethyl, propyl and butyl, etc. The alkylammonium carborane is prepared from decarborane according to either method B or method C illustrated in FIG. l. In method B, decaborane is reacted with an isocyanide of the aforementioned alkyl groups. The reaction is as follows:

BIOHM 10H12 This reaction is performed at ambient temperature and results in the insertion of a carbon atom in the boron structure to yield a truncated icosahedron unit with a carbon atom in the open face having an alkyl ammonium group dependent thereon and hydrogen atoms bridging the two pairs of boron atoms in the open face of the icosahedron.

The alkylammonium carborane is converted to the monocarbollide anion in the second step of method B by treatment with concentrated (at least about 50 weight percent) aqueous alkali metal hydroxide. This treatment can also be performed in the presence of a complex of a transition metal to prepare directly the carbollyl metal complex. The treatment with the strong base results in abstraction of the bridge hydrogens on the face boron atoms and converts the ammonium carborane into a divalent C-ammonly monocarbollide anion which can complex with transition metals. This complex can be used as a catalyst in my invention or, if desired, the carbon atom can be substituted with various groups by using the Grignard reaction hereinafter described. At least one of the boron atoms on the icosahedron base can also be substituted with a ligand by carrying out the oxidative substitution reaction also hereinafter described.

The monocarbollide anion can be obtained with a hydrogen rather than an ammonium group on the face carbon. This is achieved by fully N-alkylating the ammonium carborane with an alkyl sulfate in a strong base. This treatment is shown on FIG. 1 by the arrow that extends to the fully N-alkylated ammonium carborane shown in method C. Treatment of this material with an alkali metal hydride in anhydrous solvent, eg., tetrahydrofuran, or with concentrated (at least 50 weight percent) aqueous alkali metal hydroxide abstracts the bridging hydrogen atoms and also abstracts the ammonium group, thereby forming the trivalent monocarbollide anion.

An alternate preparation of the N-alkylated ammonly carborane is shown in method C. In this method, an alkali metal cyanide is reacted with decarborane in aqueous solution as follows:

7 The aqueous solution of the cyanoborane is passed over an ion exchange solid which causes rearrangement of the anion to the neutral C-ammonly carborane which is recovered by evaporation of the column effluent to dryness. The C-ammonly carborane can be puried from boric acid, also formed during the column treatment,

` by extraction into an ether solvent. This material can then be fully N-alkylated by treatment with an alkyl sulfate in an aqueous alkaline solution, erg., ten percent aqueous sodium hydroxide, to provide the last intermediate to the trivalent monocarbollide anion.

CARBON SUBSTITUTED CARBOLLIDE PREPARATION Asn previously mentioned,V the. carbollides can beV obtained wherein various substituents are bonded to the boron and the carbon atoms of the carbollyl cage. These derivatives are attached to the cage atoms by two center bonds. For the simplest case the groups on the cage atoms are terminally bonded hydrogen. The carbon atoms, however, can be substituted with a plurality of groups such as alkyl, eg., methyl, propyl, isopropyl, ethyl, butyl, amyl, dodecyl, hexadecyl, etc.; aryl and alkaryl, eg., phenyl, tolyl, xylyl, naphthyl, cumenyl, ethylphenyl, etc.; alkenyl, e.g., propenyl, amyl, butenyl, etc.; halo, e.g., iodo, bromo, chloro, fluoro, carboxyl, eg., carboxymethyl, carboxyethyl, carboxypropenyl, etc.

The aforementioned substituents can be formed on one or both of the carbons of the dicarborane used as the dicarbollyl precursor by use of the appropriately substituted acetylene in the synthesis of the dicarborane from decaborane as previously mentioned. The use of some substituted acetylenes and the identification of the resultant 1 and 1,2-substituted carboranes appears in Inorganic Chemistry, volume 2, No. 6, pages 1115-1119. The syntheses comprise reaction of the substituted acetylene with decaborane in an inert solvent and in the presence of a Lewis base such as acetonitrile or diethyl i sulfide. Using the appropriately substituted acetylene, the

syntheses of the following carboranes is reported: 1-ethyl carborane, l-propylcarborane, l-hexylcarborane, vinylcarborane, 1-.phenylcarborane, 1-beta-bromoethylcarborane, 1 chloromethylcarborane, 1 beta-chloroethylcarborane, 1 S2 chloropropylcarborane, l-carboranylmethyl acetate, 1 carboranylmethyl acrylate, 1 carboranylglycol diacetate, 1 carboranylethylidene diproprionate, 1 methyl 2 carboranylethylidene diproprionate, 1,2 bis(alpha-methylvinyl)carborane, 1,2- bis chloromethyl)carborane, 1,2 bis carbomethoxy) carborane, l methyl 2 bromomethylcarborane, 1,2- diisopropylcarborane, 1,2 bis (hydroxymethyl)car borane, 1 hydroxymethyl 2 ('y-hydroxy-a-propynyD- carborane, diethyl 2,2, bis (l-carboramylmethyl) malonate and 1-bromomethyl-Z-methylcarborane.

CARBON SUBSTITUTED DERIVATIVES The hydrogen bonded to the carbon of the monoor di-carborane or of the monoor di-carbollide cage exhibits the similar reactivity as the hydrogen on acetylene and accordingly a cage carbon atom can also be substituted by any of the reactions employed for substitution on acetylene. Thus, the carborane can be alkylated by reaction with an alkyl halide in the presence of a Lewis acid such as aluminum or ferric bromide or chloride; see U.S. Pat. 2,999,117; to substitute the cage carbon atoms with an alkyl or aryl group.

The cage carbons can also be substituted with a variety of groups by the Grignard reaction. In this reaction, the 1- or 1,2-halo substituted carborane or carbollide is reacted in an inert solvent, eg., ethyl ether, with magnesium to form a Grignard reagent which readily undergoes standard Grignard reactions to substitute the cage carbons. This reaction is described in the aforecited publication and in Inorganic Chemistry, vol. 2, No. 6, pages 1115-1125 (December 1963). The carboranyl Grignard reagent, eg., 1-carboranylmethylmagnesium bromide can be reacted with: (1) alkyl or alkenyl ketones or aldehydes to prepare secondary and tertiary vcarboranyl alcohols, (2) formaldehyde to prepare a primary carboranyl alcohol, or (3) alkyl, aryl or alkenyl halides to prepare alkyl, aryl or alkenyl halides to prepare alkyl, aryl or alkenyl substituted carboranes, (4) acetals to prepare alkyl carboranyl ethers, or (5) nitriles to prepare carbonyl ketones.

Examples of reactants which can be used are: formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, isobutyraldehyde, methylethyl ketone, diisopropyl ketone, benzaldehyde, crotonaldehyde, acrolein, etc.; ethyl chloride, methyl bromide, allyl bromide, chlorobenzene, amyl iluoride, chloronaphthalene, etc.; 1,1-dimethoxy ethane, 1,1-diisopropoxybutane, 1,1-diethoxy hexane, etc.; acetonitrile, acrylonitrile, benzonitrile, crotonitrile, valeronitrile, methacrylonitrile, butyronitrile, isobutyronitrile, capronitrile, etc. The choice of solvent can also inuence the product obtained from the Grignard reaction, eg., it has been reported that when allyl bromide was reacted with the Grignard reagent, 1-carboranylmethylmagnesium bromide, the normal reaction yields 4-(1carboranyl)-1- butene; however, with tetrahydrofuran as the solvent, 1- allyl-2-methylcarborane is obtained.

The carborane can also be reacted Iwith alkyl and aryllithium reagent, e.g., butyl or phenyl lithium, at temperatures from 0 to 30 C. to provide the l-lithium and 1,2-dilithium carboranes which can then be reacted to produce carboranyl acids, carbinols and halides. To illustrate, the contacting of dilithium dicarborane with carbon dioxide at temperatures from `0" to 25 C. forms the lithium salt of 1,2-carboranedicarboxylic acid from which the acid can be formed by acidification. Contacting the lithium carborane with an alkylene oxide, eg., ethylene oxide, yields the hydroxyalkyl derivative, e.g., 1 ,2-bis(hydroxyethy1) -carborane The carboranediformyl halides can be obtained by reaction of the lithium salt of 1,2-carboranedicarboxylic acid with excess oxalyl chloride. The resultant acid chloride can then be reacted with alkyl, cycloalkyl and alkenyl alcohols to form esters of the 1,2-carboranedicarboxylic acid. The disubstituted carboranes have also been found to exhibit a strong tendency to form 1,2-exocyclic derivatives. Treatment of the bis- (hydroxy)carboranes with an acid such as concentrated sulfuric at temperatures from to 175 C. forms cyclic ethers. Upon heating to about 25W-300a C. the bis(2carboxyl-carboranylmethyl) ether form 2 moles of a carboranyl lactone, B10H10CCH2OC(O)C; and the 1,2- dicarboranedicarboxylic acid form a cyclic anhydride by contacting with dehydrating agents such as thionyl chloride in the presence of sodium carbonate.

BORON SUBSTITUTED DERIVATIVES The hydrogen bonded to the boron of the icosahedral cage is also bonded with a two-center bond and these hydrogen atoms can be replaced with Ivarious substitutents. Simple halogenation of the carborane or carbollide anions will first halogenate the boron atoms to provide carbollides containing up to 10 bromo, uoro, chloro or iodo atoms. A description of the halogenation as applied to chlorination of dicarborane appears in Inorganic Chemistry, vol. 2, No. 6, pages 10924096 (December 1963). A similar halogenation technique can be applied to the monocarborane to produce its halogenated derivatives. This reaction comprises contacting the carborane in an inert solvent with gaseous halogen, e.g., chlorine. The boron atoms are halogenated rst before halogenation of the carbon atom or atoms. The degree of lialogenation can be controlled by limiting halogen concentration or the solvent, eg., carbon tetrachloride, to precipitate the halogenated carboranes as the di, tri, tetra, hexa, octa, deca and undeca-halocarborane.

The carbollide can also be obtained having one or two of the cage boron atoms in the upper plane, i.e., atoms 4, 8 and 7 of the dicarbollide or atoms 4, 8, 7 and 2 of the monocarbollide substituted -with an alkyl, aryl, alkaryl, aralkyl, alkenyl, aralkenyl, etc. group. A procedure that can be used to prepare the boron substituted derivatives comprises reforming the carborane from the carbollide anion using an organic boron halide. The resultant boron substituted carborane can then be treated with strong base or alkali metal halide to abstract a boron atom from the cage and form a boron substituted carbollide. This procedure can be repeated to prepare a di-substituted carbollide having two of the open face borons substituted with an organic group. This procedure is illustrated in the examples and briefly comprises reaction of a soluble salt, eg., alkali metal salt of the carbollide anion with an organic substituted boron halide. This reaction is performed at ambient conditions of temperature and pressure and proceeds as follows:

wherein R contains from 1 to about 12 carbons and is alkyl, alkenyl, aryl and halo, carboxy or sulfo derivatives thereof.

Examples of suitable R groups are methyl, carboxymethyl, chloromethyl, ethyl, isopropyl, amyl, dodecyl, octadecyl, phenyl, p-bromophenyl, 2-lauryl-4-sulfophenyl, Xylyl, tolyl, naphthyl, dichlorophenyl, vinyl, allyl, butenyl, etc. The resultant boron substituted carborane can then be reacted in the manner previously described to abstract a boron hydride from the icosahedron structure and thereby form a B-substituted carbadodecahydroundecaborate ion with the organic substituent on a boron atom in the open face of the truncated icosahedron. Repeated insertion of a like or differently substituted boron atom provides a route to B,B-disubstituted carbollide ions.

As previously mentioned, one of the boron atoms in the face of the truncated icosahedron carbollide ion can also be substituted with a suitable ligand. Any of the aforementioned ligands can be employed for this substitution which is an oxidative substitution performed by reacting a salt of the carbollide ion or the carbadodecahydroundecaborate ion with an oxidizing agent such as ferrie chloride, cupric chloride, etc., in the presence of the ligand. This treatment results in oxidation of a hydrogen of a boron atom in the face of the truncated icosahedral cage with reduction of the ferric or cupric chloride to ferrous or cuprous chloride and substitution of the ligand on a boron atom. The reaction illustrated with potassium carbadodecahydroundecaborates is as follows: KB9C2H12 2FC13 l- BQCZHU ligand-l-ZFeClz-l-KCl-l-HCl The substitution occurs on the boron atoms in the face of the truncated icosahedral carbollide ion. Two isomers are formed from the dicarba homolog and these isomers are symmetrical or asymmetrical depending on the location of the substituted boron atom on the face of the truncated icosahedron. Both isomers of the monocarba homolog are asymmetric. This substitution can be performed with any of the ligands mentioned in the section hereinafter entitled Ligands The following is a listing of some of the carbollide ions which can be formed in this manner: 8-tetrahydrafuran-(3)-l,2dicarbollide; 4- tetrahydrafuran-l,Z-dimethyl-1,2-dicarbollide; S-pyridine- (3)-l,2dicarbollide; 8 tetrahydrafuran-(3)-l-monocar bollide; 4-pyridine(3)-1methyll-monocarbollide; 7-diethylsulde-(3 )-1,2-dimethyl-1,2-dicarbollide; 4-triphen1- ylphosphine( 3 -l,2dicarbollide; 4-methylcyanide- 3 -lphenyl, 1,2-dicarbollide; etc.

LIGANDS Ligands as dened herein for substitution on a boron atom of the carbollide ion by use in the oxidative sub- 10 stitution reaction previously mentioned or for complexing with the transition metals to form a mixed vr-ligand-w-carbollyl metal complex as hereinafter described comprise electron contributing reactants which have at least one atom with an unshared electron pair which is available for coordinate covalent or multicenter bonding. Examples of ligands include the halogens and compounds of nitrogen, oxygen, sulfur, arsenic, antimony, bismuth and phosphorous wherein the indicated element has a valence pair of unshared electrons. The reactants can contain only one of these atoms per molecule (monodentate); two atoms (bidentate), or a plurality of centers (polydentate).

Examples of ligands include:

(l) Halides, e.g., chloro, bromo, fluoro and iodo;

(2) Oxygen compounds, e.g., water, carbon monoxide; alkyl, aryl and alicyclic hydroxy compounds such as alkoxys, e.g., methoxy, ethoxy, isopropoxy, dodecoxy, penoxy, xyloxy, naphthoxy, cyclohexoxy, hexoxy, etc.; alkyl carbonyl or carboxyl compounds such as acetyl acetonate; aliphatic beta-iminoketones, e.g., 1 methyl 3- iminopropanone, 3 isopropyl 3 iminopropanone, 1,3- dibutyl 3 iminopropanone, 3 isoamyl 3 iminopropanone, etc.; aliphatic hydroxy ketones and hydroxy aldehydes such as 2 hydroxy 5 acetyl acetophenone, 2 hydroxy 4 butyl benzaldehydle, etc.; alkyl and aryl peroxides, e.g., benzoyl peroxide, ethyl methyl peroxide, acetyl benzoyl peroxide, etc.; hydroxymonobasic, hydroxydibasic and dibasic aliphatic acids, ammonium and alkali metal salts and alkanol esters thereof such as glycolic acid, latic acid, betahydroxy butyric acid, alphahydroxy butyric acid, glyceric acid, gluconic acid, maleic acid, oxalic acid, tartaric acid, citric acid, etc.; heterocyclic oxy compounds having from 3 to about 7 members in the heterocyclic ring and including the following parent compounds, the ring position isomers thereof and the alkylated derivatives thereof wherein from l to all the ring carbons are substituted with an alkyl or alkenyl group containing up to about 6 carbons, eg., ethylene oxide, propylene oxide, styrene oxide, 2,3-epoxybutane, trimethylene oxide, 1,3-epoxyheptane, furans, tetrahydrofurans, pyrans, tetrahydropyrans, pyrones, dioxins, oxathioles, ixoxazoles, oxazoles, oxadizoles, oxepins, oxa- Zines, benzopyrans, benzopyrones, benzofurans, benzoisofurans;

(3) Nitrogen compounds such as nitric oxide, ammonia, alkyl and aryl amines such as methylamine, diethylamine, isopropyl amine, trimethylamine, amylamine, dodecanol amine, cyanogen, hydrogen cyanide and aliphatic or aryl nitriles, e.g., acetonitrile, propionitrile, isobutyronitrile, acrylonitrile, adiponitrile, benzonitrile, terephthelonitrile, etc.; alkyl, cycloalkyl and aryl iSocyanates such as ethyl isocyanate, isobutyl isocyanate, phenyl isocyanate, cyclohexyl isocyanate, etc.; alkylenediamines, N alkylalkylenediamines, N,N alkylalkylenediamines and alkylenediaminecarboxylic acids and their salts such as ethylenediamine, N methylethylenediamine, N ethylethylenediamine, N,N di n propylethylenediamine, propylenediamine, 2,3 dimethyl- 2,3 diaminobutane, trimethylenediamine, 2. hydroxy- 1,3 diaminopropane, tetramethylenediamine, pentamethylenediamine, ethylenediamine N,N dipropionic acid, N hydroxyethylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, etc.; heterocyclic nitrogen compounds having from 3 to 7 membered rings containing up to 3 or 4 heteroatoms at least one of which is nitrogen including the parent compounds listed below their ring position isomers and the alkylated derivatives thereof wherein from 1 to all the ring carbon atoms are substituted with an alkyl or alkenyl group containing up to about 6 carbons, eg., ethylene imine, trimethylene imine, pyrroles, isopyrroles, pyrazoles, triazoles, oxatriazole, pyridines, pyridazines, pyrazines, piperazine, triazines, morpholine, azepine, indole, pyrindine, quinoline, isoquinoline, etc.; polyhetero- 11 cyclic amines having at least one nitrogen in a bridgehead position such as 1,2,4 triazabicyclo (l.l.1.)pentane, thia 1,6 diazabicyclo(2.l.1)hexane, 1,4 diazabicyclo- (2.2.2)octane (triethylene diamine), 1,3,5,7 tetrazabicyclo (3.3.1) nonene (pentamethylenetetramine), l,3,5,7 tetrazatricyclo(3.3.l.l)decane (hexamethylenetetramine), etc.;

(4) Sulfur compounds such as sulfur dioxide, carbon disulfide, and aliphatic mercaptans and sulfides such as methyl mercaptan, dodecyl mecaptan, dimethyl sulde, diethyl sulde, diisopropyl sulfide, dibutenyl sulfide, diamyl sulfide, ethyldecyl sulfide, methyldodecyl sulfide; etc.; heterocyclic suldes having from 3 to about 7 membered rings containing up to about 3 heteroatoms at least one of which is sulfur and including the parent compounds listed below, their ring position isomers and the alkylated derivatives thereof wherein from l to all the ring carbons are substituted with an alkyl or alkenyl group having up to about 6 carbons, e.g., ethylene eposulde, thiophenes, tetrahydrothiophenes, thiobiazolones, thiobiazolines, thiodiazoles, thiodiazolidines, azosulnes, piazothioles, thobiazolines, thionessals, thiochroman, bithiophenes, thiopins, thionaphethenes, iso thionaphthenes, oxathioazines, etc.;

(5) Organic compounds containing at least one trivalent atom of phosphorus, bismuth, arsenic or antimony having an unsheared pair of valence electrons. These compounds can be described by reference to empirical formulae as follows:

lERa

(R)2ER'E(R)2 wherein:

E is a trivalent phosphorous, bismuth, arsenic or antimony atom;

R is hydrogen, alkyl and cycloalkyl from 1 to about 8 carbon atoms, aryl from 6 to about 8 carbons or the halo, amino and alkoxy derivatives thereof; and

R is alkylene from l to about 8 carbons.

Examples of suitable ligands of the preceding formulae include: trimethyl phosphine, triethyl arsine, tn'isopropyl stibine, diethylchloro phosphine, triaminobutyl arsine, ethyldiisopropyl stibine, tricyclohexyl phosphine, triphenyl phosphine, triphenyl bismuthine, tri(o tolyl)phosphine, phenyldiisopropyl phosphine, phenyldiamyl phosphine, diphenylethyl phosphine, chlorodixylyl phosphine, chlorodiphenyl phosphine, tris(diethylaminoethyl) phosphine, ethylene bis (diphenyl phosphine), hexamethylene bis- (diisopropyl arsine), pentamethylene bis (diethyl stibine), etc.;

(6) Unsaturated compounds such as the unsaturated hydrocarbons including unsaturated alicyclic and aliphatic hydrocarbons of 2 to about 15 carbons which form pi bonds with the metals. Examples of these are alkenes e.g., ethylene, propylene, butene-l, butene-2, pentene, isooctene, decene-l, dodecene-2, octadecene, etc.; alicyclics such as Cyclopentadiene, dischlorocyclopentadiene, uorene, cycloheptatriene, tetraphenylcyclobutadiene, cyclopentadiene, etc.; aromatics such as benzene, naphthene, oanisine, thiophene, indene, xylene, toluene, cumene, etc.

Metals which will readily form complexes with the carbollide ions comprise any of the metals which in their metal or ionic state have available orbitals of 1r-symmetry. Orbitals of 1r-symmetry are the d and p orbitals. The metal is the electron donating component of the complex, so any metal Which in the metallic or ionic form can donate at least one electron and has d and p orbitals can be used, These include the alkaline earth metals, all the transition metals, as well as the metals of Groups III-A, IV-A, V-A and VI-A. Metalloids such as phosphorus, arsenic, silicon and tellurium can also be used. In this respect, the car- 12 bollide is closely similar to cyclopentadiene ion (C5H5-), which likewise readily forms complexes with the transition metals. The carbollyl-metal complex is formed by admixing a soluble salt or soluble complex of the metal with a solution of the carbollide anion. Examples of metals `which readily form carbollyl metal complexes with the carbollide ion include metals of Groups I-B, copper, silver, gold; lI-B, zinc, cadmium, mercury; III-A, aluminum, gallium, indium, thallium; beryllium of Group II-A; IV-A, germanium, tin and lead; IV-B, titanium, zirconium, hafnium; V-A, antimony, bismuth; V-B, vanadium, niobium, tantalum; VI-B, chromium, molybdenum, tungsten; VIIB, manganese, technetium, rhenium; VIII including the iron subgroup comprising iron, cobalt and nickel, the palladium subgroup including ruthenium, rhodium and palladium and the platinum subgroup including osmium, iridium and platinum.

Any of the preceding metals can be complexed with a carbollide anion by dissolving a suitable salt of the metal or a complex of the metal with one of the aforementioned ligands in a solvent and adding thereto a soluble salt of the carbollide salt or a solution of the salt. As apparent to those skilled in the art, the choice of the anion associated with the transition `metal depends upon the solubility characteristics of the particular metal. Thus halide salts including bromides, chlorides, uorides and iodides of the appropriate metals can be used, such as palladous chloride, ferrie chloride, cupric chloride, titanium tetrachloride, etc. The nitrates can be employed such as silver nitrate, cadmium nitrate, etc.; the sulfates of the metals such as mercurio sulfate, manganese sulfate, indium sulfate, etc.

Complexes of the metals with various ligands can also be employed as the source of the metal for the formation of the carbollyl metal complex. Any of the aforementioned ligands that form soluble complexes with any of the aforementioned ligands that form soluble complexes with any of the aforementioned metals can be employed. Examples of metal complexes which can be used include the following: zinc acetyl acetonate, ammonium tetrabromocadate (II), potassium tetrathiocyanomercurate (II), vanadium hexacarbonyl, chromium hexacarbonyl, molybdenum hexacarbonyl, tungsten hexacarbonyl, dimanganese decacarbonyl, potassium hexauororhenate (IV), iron pentacarbonyl, hexacarbonyl-w-dicarbonyldicobalt, nickel tetracarbonyl, ferrocene, sodium dicyanocuprate (I), zirconium acetyl acetonate, ammonium hexauorozirconate (IV), etc., dibutoxydiphenyltitanium, diethyltitanium, dichloride, (benzylcyclopentadienyl)titanium tribromide, oxybis (dichlorocyclopentaienyltitaniurn), fluorenylzirconium, trichloride, ethylene bis(oxydibromofluorenyl zirconium), bis(iaenzene) zirconium, (ethylcyclopentadienyl) hafnium triuoride, indenylhafnium triuoride, diphenylvanadium chloride, 1r cycloheptatrienylcyclopentadienylvanadium, tetracarbonylfiuorenylvanadium, bis(benzene) vanadium, tetracarbonylcyclopentadienylniobium, bis(cyclopentadienyl) niobium trichloride, tetracarbonylcyclopentadienyltantalum, dibenzylchro mium chloride, tri-a-naphthylfhromium, di-o-anisylchro- `miur-n, tricarbonylcyclopentadienylhydridochromium, tris- (methanethiolato bis cyclopentadienylchromium cyclopentadienyldinitrosylchromiurn chloride, tricarbonylthiophenechromium, lithium tricarbonylcyclopentadienylmolybdate, bis(idenyl) molybdate trichloride, tricarbonylcyclopentadienyltungsten hydride, bis(benzene) tungsten, drphenylmanganese, acryloylpentacarbonylmanganese, tricarbonylcyclopentadienyltechnetium, bis (cyclopentadienyl)rhenium hydride, dibenzyliron, dicarbonylcyclopentadienyliron hydride, carbonyldicyancyclopentadienylferrate, ferrocene, cyanoferrocene, ferrocenesulfonic acid, dicarbonyldieyancyclopentadienylruthenium hydride, bis- (cyclopentadienyl)ruthenium, cyclooctadienylruthenium chloride, osmocene, acetyltetracarbonylcobalt, dinitrosyl- (tricyanomethyl)cobalt, cobaltocene, carbonyl tris(tri phenyl)rhodium hydride, bis(cyclopentadienyl)iridium- (III)chloride, diphenylnickel, nickelocene, bis(acrolein) nickel, di-,u-chlorodichlorobis(ethylene)dipalladium, bis- (cyclopentadienyl)palladium, allylcyclopentadienylplatinum, dichlorobis(ethylene) platinum, etc.

COMPLEX PREPARATION The metal complex can be formed by admixture of a solution of the carbollide ion formed as previously mentioned, with a solution of a salt or ligand complex of the particular metal. As previously mentioned, `when aqueous concentrated base is used for the boron abstraction of the dicarborane, a metal ligand complex is preferably present, so this preparation results in a one-step synthesis of the carbollyl metal complex from the carborane. Generally, however, the carbollide anion is prepared first and the carbollyl metal complexes are formed from a solution of the dicarbollide anion or from the monocarbollide anion.

A carbollyl metal complex can be prepared by simply admixing a soluble salt or ligand complex of the metal with a soluble form of the carbollide anion in an inert solvent. A suitable inert solvent that can be used in the preparation is tetrahydrofuran. Other solvents include any of the solvents hereinafter described under the section entitled Solvents. To this solvent can be added a soluble salt, e.g., -ferrous chloride and a soluble salt of the carbollide anion such as sodium carbollide is thereafter added. Preferably the carbollide solution is prepared in tetrahydrofuran and thereafter added to a tetrahydrofuran solution of the indicated metal salt. The resultant carbollyl metal complex can be crystallized by evaporation of the solvent to obtain a crystalline residue. When the carbollyl metal complex is an anion and is present as an alkali metal salt it c an be dissolved in water and purified by liltration through a suitable adsorbent, eg., diatomaceous earth. The carbollyl metal complex can be recovered from the aqueous solution by precipitation with a suitable base exchange material, e.g., an aqueous solution of a tetramethyl ammonium salt. When this procedure is performed in the absence of any free ligand, a bis complex or a di-1r-carbollyl metal complex is formed. The structure of such a bis-carbollyl metal complex is illustrated in FIG. 3. The complex can also be formed in the presence of an excess `quantity of another ligand such as any of the aforementioned ligands which are capable of forming bonds with transition metals. Accordingly, the formation of the carbollyl complex in the presence of any of the aforementioned ligands would prepare the mono- 1r-carbollyl mono-ligand metal complex. Thus reaction of the metal salt with the carbollide ion in the presence of a cyclopentadianide ion would form the complex as illustrated in FIG. 5; reaction of the metal salt, the carbollide ion, and tetraphenylcyclobutadiene would prepare the complex illustrated in FIG. 7. Use of the metal carbonyls as the source of the metal would similarly form the carbonyl-mono-vr-carbollyl metal complex illustrated in FIG. 5.

The carbonylcarbollyl metal complexes also dimerize in a manner similar to the dimerization of the metal carbonyls. The carbonyldicarbollylferrate (III) will dimerize to carbonyldicarbollyliron(III)-p-dicarbonyl carbonyldicarbollyliron(III), a divalent anion. An example of another dimer is carbonyldicarbollylcobalt(III) p. dicarbonylcarbonyldicarbollylcobalt(III), also a divalent anion.

Examples of carbonyl metal complexes which can be formed by the preparation disclosed herein are listed in the following table. For simplicity, when the complex has a net negative charge, the cation associated with the complex ion is not included. Examples of such are the alkali metal, ammonium, organic ammonium cations, e.g., sodium, lithium, potassium, ammonium, tetramethylammonium, ethylammonium, etc. Examples of anions associated with cationic complexes are halides, e.g., chlorides, uoride, etc.; nitrate, sulfate, phosphate, etc.

cyclopentadienyldicarbollyliron(III) cyclopentadienyldicarbollylferrate (II) bisdicarbollyferrate (II) (III) cyclopentadienyldicarbollylcobalt (III) cyclop entadienyldicarbollylnickel (III) cyclopentadienyldicarbollylnickelate (II) bisdicarbollylcuprate (II) (III) bisdicarbollylchromium (IV) bisdicarbollylchromate (III) tricarbonyldicarbollylmanganese (II) tricarbonyldicarbollylmanganate (I) tricarbonyldicarbollyhnolybdenum (II) bisdicarbollylmolybdate (II) (III) bisdicarbollylmolybdenum (IV) tricarbonyldicarbollyltungsten(II) bisdicarbollyltungstate (II) (III) bisdicarbollyltungsten(IV) tricarbonyldicarbollylrhenium (II) tricarbonyldicarbollylrhenate (I) bisdicarbollylpalladium(IV) bisdicarbollylpalladate(II) (III) bismonocarbollylferrate (III) bismonocarbollylnickelate (1V) bis-C-aminomonocarbollylnickelate (IV) bis-C-ammonylmonocarbollylnickel (IV) bismonocarbollylmagnesate tris triphenylphosphine) monocarb ollylyttrium bisdicarbollyltitanium (IV) tris (tri-n-butylphosphine) dicarbollylvanadium (III) (IV) (V) chloride bisdicarbollylvanadium( IV) tris diethylsulde monocarbollylosmium (III) bisdicarbollylrhodate (II) (III) trichloro dicarb ollylpalladium bisdicarb ollylplatinum (IV) triethylenemonocarbollyl gold (III) 'bisdicarbollylzincate (II) bismonocarbollylaluminate (III) hexa (dimethylsulfoxo monocarbollylaluminum (III) bisdicarbollyltin (IV) bismouocarbollylbismuthate (III) cyclopentadienyl-B-ethoxydicarbollyliron (III) prosphate For solubility in hydrocarbon fuels, I prefer to select the electroneutral complexes, i.e., those having a net charge of zero. By proper selection of the ligands, a neutral complex can be achieved with most metals. To illustrate, the cyclopentadiene ion (-1) and dicarbollide ion (-2) ligands can be used with metals having a valency of +3. With metals having a valency of +2, neutral ligands such as carbon monoxide are used with the dicarbollide ion. Metals having a +4- valency can be complexed into a neutral species with two dicarbollide 2) anions or with a mononegative ligand such as a cyclopentadiene ion and a monocarbollide ion (-3) ligand. Metals of +5 valency can be complexed with a mixture of monocarbollide ion (-3) land dicarbollide ion (-2) ligands. Metals of +6 valency can be complexed into neutral species as the bismonocarbollyl metal. The carbollides can be prepared with a range of valencies from -1 to -3 and this flexibility also permits synthesis of electroneutral complexes. The dicarbollide anion is divalent while the monocarbollide ion is trivalent; however, ligand substitution of a hydride from a face boron atom as previously described, permits preparation of the -1 diarbollide ion and the -2 monocarbollide ion.

Most of the transition metals are multivalent and retain this characteristic in the carbollyl complexes. Accordingly, another method to attain electroneutral complexes is to reduce or oxidize the metal complex to obtain a neutral species. Treatment at temperatures from 0-500 C. with oxygen can effect a change to a more positive net charge on the complex. Treatment at these temperatures with a reducing agent, eg., hydrogen, hydrazine, etc., will effect a change t0 a more negative net charge on the complex. In this manner, electronegative complexes can Ibe rendered electroneutral and highly soluble in hydrocarbons.

SOLVENTS The carbollyl metal complexes are stable and soluble in a variety of solvents. The neutral species are soluble in organic solvents while the ionic species are soluble in Iaqueous and polar organic solvents. Since the carbollyl metal complexes are highly electrophillic, solvents that are readily oxidized such as amines, alcohols, aldehydes, sulfides, etc., should be used with caution. Examples of other suitable solvents are hydrocarbons, halogenated hydrgafbons. ketgnss, esters @there amitiee sarboxyli? acids, nitriles, etc.

Hydrocarbons useful as solvents include the aromatic, aliphatic and alicyclic hydrocarbons such as benzene, toluene, xylene, cumene, ethylbenzene, pseudocumene, durene, naphthalene, a-methylnaphthalene, indene, butane, pentane, hexane, isooctane, decane, Z-ethyldodecane, cyclohexane, cycloheptane, methylcyclopentane, ethylcyclohexane, dimetrylcycloheptane, cyclooctane, etc. Mixtures of the aforementioned as well as petroleum distillates can also be suitable solvents such as naphtha, kerosine, etc.

Halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride, dichlorodifluoroethane, chlorobutane, diuoropropane, chlorocyclopentane, iodobenzene, dibromoethane, dichlorobenzene, etc., can also be suitable solvents. l

Ketones such as acetone, methylethyl ketone, diisopropyl ketone, methylamyl ketone, furan, isopropylfuran, valerolactone, methyldecyl ketone, pyran, ethylpyran, pyrone, benzofuran, benzopyran, dioxane, etc., can be used as solvents.

Esters of aromatic or alkanoic acids with saturated alcohols or phenols can also be used such as ethyl formate, methyl acetate, ethyl acetate, n-propyl formate, isopropyl acetate, ethyl propionate, n-propyl acetate, secbutyl acetate, isobutyl acetate, ethyl n-butyrate, n-butyl acetate, isoamyl acetate, n-amyl acetate, ethyl form-ate, ethylene glycol diacetate, glycol diformate, cyclohexyl acetate, furfuryl acetate, isoamyl 4butyrate, diethyl oxalate, isoamyl isovalerate, methyl benzoate, diethyl malonate, valerolactone, ethyl benzoate, methyl salicylate, n-propyl benzoate, n-dibutyl oxalate, n-butyl benzoate, diisoamyl phthalate, dimethyl phthalate, diethyl phthalate. benzyl benzoate, n-dibutyl phthalate, etc.

Ethers can be used such as diisopropyl ether, di-n-butyl ether, ethylene glycol diisobutyl ether, methyl o-tolyl ether, ethylene glycol dibutyl ether, diisoamyl ether, methyl p-tolyl ether, methyl m-tolyl ether, dichloroethyl ether, ethylene glycol diisoamyl ether, diethylene glycol diethyl ether, ethylbenzyl ether, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, ethylene glycol dibutyl ether, ethylene glycol diphenyl ether, triethylene glycol diethyl ether, diethylene glycol di-n-hexyl ether, tetraethylene glycol dimethyl ether, tetraethylene glycol dibutyl ether, etc.

Another class of organic solvents that have sufficient solvency are various a-ides such as formamide, dimethyl formamide, ethylisopropyl formamide, acetamide, n-phenylacetamide, N,N dipropylacetamide, isobutyramide, N-ethylisobutyramide, isovaleric amide, N,Ndirnethyliso valeric amide, isocaprylic amide, N,N-methylncaprylic amide, N-propylene-n-heptanoic amide, isoundecylic amide, etc.

Carboxylic acids include formic, acetic, propionic, butyric, pentanoic, hexanoic, heptanoic, octanoic acids, benzoic, toluic, phthalic acids, etc. Of these, the fatty carboxylic acids having from about 2 to about 8 carbons are preferred. The carboxylic acids are not entirely inert under the oxidation conditions in that the carboxylic acids add to the olefin double bond to form beta-acyloxy compounds. These materials, however, can be readily pyrolyzed to recover lboth the carboxylic acid for reuse as the reaction medium and the desired unsaturated acid.

Nitriles such as acetonitrile, isopropionitrile, valeronitrile, capronitrile, etc., can also be used as solvents for the carbollyl metal complexes.

HYDROCARBON BASE STOCKS The compositions of this invention comprise a major proportion of a hydrocarbon base stock which includes fuels as well as lubricants. Since the carbollyl metal complexes are combustion improving agents and when added to hydrocarbons reduce smoke and carbon formation and prevent: gum depositstthese materials can be used in cornbination with Vany Vhydrocarbon fuel'includ'ng hydrocarbon gases, liquefied petroleum gases, liquefied methane gas, liquefied butane, pentane, etc., with internal combustion engines, fuels such as kerosene, jet fuel, diesel fuels, gas oils, burner oils, etc. The use of the carbollyl metal complexes in any of the aforementioned can be combined with other commonly employed additives such as antioxidants, rust inhibitors, dyes, deposit modifiers, scavengers, or other anti-knock agents or cetane number improvement additives.

When employed in motor fuels, the base stock can include all types of hydrocarbons such as the normal and iso parafiins, olefins, cycloaliphatics containing parafinic or olefinic sidechains, aromatics containing paraffinic or olefinic sidechains, etc. The base stock can be obtained from straight run or processed mineral oil including thermally or catalytically cracked, reformed, hydrocracked, hydrofined, or other processed mineral oil.

The boiling range of the base stock depends on the intended use of the base stock as a fuel. When employed as a fuel for internal combustion engines, the base stock has an initial boiling point from 0 to about 100 F. and a final boiling point of about 385 to about 475 F. This boiling point temperature varies somewhat with the use, e.g., aviation gasoline commonly has a boiling point range from about to about 350 F. When used as an additive in a fuel for compression ignition engines, the hydrocarbon base stock commonly has a boiling point range from about 400 to about 750 F. When used as a jet fuel, the boiling point range is commonly from about 400 to about 625 F. Burner fuels generally have boiling point ranges from about 450 F. to about the equivalent of l000 F., atmospheric boiling point temperature or higher. Commonly a preferred fuel for burner operations is a heavy gas oil distillate or the equivalent having a maximum boiling point of about 850 to 1000 F. at atmospheric pressure. Residual oils, however, are also ernployed for fuels in burners and accordingly these residuals having initial boiling points from about 650 can also be employed as the base stock for the compositions containing the carbollyl metal complexes of my invention.

The hydrocarbons can contain any of the congeric impurities associated with mineral oils. Common impurities include sulfur and nitrogen impurities which are present in the distillate fuels as well as the residual fuels. Also found in many of the residual fuels are trace amounts, up to about parts per million, of metal contaminants including vanadium, nickel, iron, copper, etc. These base stocks can contain from 0.1 to about 3 weight percent sulfur and/or nitrogen and up to about 1.0 weight percent of any of the aforementioned metal contaminants. The hydrocarbon base stock can be refined as is commonly practiced to reduce the level of the aforementioned impurities and in particular the distillate fuels can be refined to reduce the sulfur and nitrogen contents to less than about 0.01 and less than about 0.001 weight percent, respectively, by the various refining processes.

The carbollyl complexes of any of the aforementioned metals find particular utility when used as anti-knockj agents in internal combustion fuels as well be apparent from the examples hereinafter set forth. Examples of particularly useful metals are: aluminum, cadmium, beryllium, bismuth, cobalt, copper, lead, magnesium, manganese, mercury, molybdenum, nickel, tellurium, thallium, tin, tungsten, zinc and iron.

The additives can be incorporated in the base hydrocarbon stock by the direct addition thereto or by incorporating the additives in a hydrocarbon solvent such as kerosene, toluene, hexane, etc., or in any other suitable solvent such as carboxylic acids, e.g., acetic, propionic, hexanoic, etc.; alkyl and aryl sulfoxides and sulfones such as dimethyl sulfoxide, methylbenzyl sulfone, etc.; amides such as formamide, dimethylformamide, isocaprylicamide, etc.; alkyl and aryl ketones such as acetone, diisopropylketone, etc.; ethers such as diisopropylethers, ethyleneglycol diisoamyl ether, etc.; esters such as ethylacetate, isoamylvalerate, propylacetate, etc. The carbollyl metal complex can be dissolved in the solvent at any desired concentration up to about its saturation in the particular solvent chosen. Generally these concentrations will be from about to about 75 weight percent of the metal carbollyl complex in the particular solvent. The amount of complex in the hydrocarbon fuel can be Widely varied from about 0.0005 to about 5 weight percent, generally from about 0.01 to about 1.5 weight percent.

The carbollyl metal complexes can also be employed in lubricants to serve as extreme pressure agents. When employed in this embodiment of the invention, the carbollyl metal complex serves as a convenient carrier for providing a stable form of the extreme pressure metal lubricant. While any of the aforementioned metals can be used for this purpose, metals useful in this embodiment for complexing with the carbollide ion include mercury, arsenic, antimony, gallium, indium, lead, thallium, tin, zinc, etc.

The following examples will illustrate the preparation of the various additives useful in accordance with my invention:

Example l illustrates the preparation of carborane;

Example 2 illustrates the preparation of bromomethylcarborane;

Example 3 illustrates the preparation of methylcarborane;

Example 4 illustrates the preparation of dimethylcarborane;

Example 5 illustrates the preparation of diphenylcarborane;

Example 6 illustrates the isomerization of phenylcarborane;

Example 7 illustrates the preparation of a C-ammonylmonocarborane;

Example 8 illustrates an alternate preparation of a C- ammonylmonocarborane;

Example 9 illustrates the preparation of (3)1,2- and (3)l,7-dicarbadodecahydraundecaborate anions from the carboranes of the previous examples;

Example 10 illustrates the preparation of dicarbollide anions;

Example 1l illustrates the preparation of B-ligand substituted 1,2-dicarbadodecahydraundecaborane and its C- substituted derivatives;

Example l2 illustrates the preparation of the dicarbollyl metal complexes.

Example 13 illustrates the preparation of a monocarbollide and the simultaneous formation of a carbollyl metal complex therefrom;

Example 14 illustrates hydrocarbon motor fuels containing the carbollyl metal complexes;

Example 15 illustrates hydrocarbon burner fuels containing the carbollyl metal complexes;

Example 16 illustrates hydrocarbon jet fuels containing the carbollyl metal complexes;

Example 17 demonstrates the anti-knock properties of the carbollyl metal complexes in a gasoline.

18 EXAMPLES Example l-Preparation of carborane This example illustrates the preparation of 1,2-dicarbaelovododecaborane (l2) from decaborane and acetylene. The preparation is performed in a one-liter round-bottom, three-necked flask which is fitted with an automatic temperature control device in one of the necks, a sparkfree stirring motor with a stirring rod extending through the center neck, and a water-cooled condenser attached to the remaining neck. The condenser connection has a concentric tube used for introduction of acetylene and this tube is extended to beneath the liquid level of the reactants in the round bottom flask. The Water-cooled condenser is placed upright for total reflux and the upper end of the condenser is fitted with a U-shaped, Dry Ice cooled condenser and the gases from the Dry Ice condenser are passed into an empty milliliter Erlenmeyer flask and then below the liquid level of a similar flask partially filled with oil.

The gas introduction train consists of a nitrogen cylinder and an acetylene cylinder which are manifolded into a purification train comprising a first 1000 milliliter Erlenmeyer flask and then three 500 milliliter round-bottom flasks connected in series having gas introduction tubes at the bottom of the flask fitted with extra coarse gas dispersion tubes and filled from 1/3 to 1/2 with concentrated sulfuric acid. The gas exit from the last purification flask is passed to an empty 1000 milliliter IErlenmeyer vessel and then to the base of a column three feet in height that is packed with a mixture of potassium hydroxide and a drying agent such as anhydrous calcium sulfate. The top of the column is connected to another empty 1000 milliliter Erlenmeyer flask and the gases are removed from this Erlenmeyer flask and passed to the tube extending through the neck of the 1000 milliliter reaction vessel. The empty Erlenmeyer flasks are employed. to serve as traps for liquids which may inadvertently back up through the system. The empty trap between the sulfuric acid and the potassium hydroxide column is used to collect any sulfuric acid foam from the last purification vessel.

The system is thoroughly dried and flushed with nitrogen before the reagents are introduced. Thereafter 100 grams of decaborane which has been purified by Sublimation or recrystallization from a hydrocarbon such as heptane is dissolved in 200 milliliters of n-propyl ether which has been freshly distilled from a mixture containing sodium and benzophenone. The solution is placed in the 1000 milliliter 3-necked flask and 200 milliliters of diethyl sulfide which has been dried by passage over a dehydrated 4-angstrom molecular sieve is thereafter added. Nitrogen is then passed through the flask while the solution is stirred for three hours at 40 C. and then the temperature is raised to 65 o67" C. and maintained at this temperature for two hours. Thereafter the flask contents are heated to the temperature of 85i2 C. and 7 mols of acetylene are passed through the purification train and into the reaction vessel over a period of 35 hours. On completion of the reaction the solution has a pale yellow to light orange color.

The reactants are then cooled to room temperature and the reaction mixture is transferred to a one-liter, roundbottom, single-necked flask and the diethyl sulfide and npropyl ether solvent is removed in a vacuum evaporation step. The flask is rotated continuously during the evaporation and is heated with a steam bath. The volatiles are condensed and collected in a Dry Ice trap. Upon removal of the solute and diethyl sulfide, the product is a light brown semisolid. The solid is dissolved in milliliters of benzene and the solution is then transferred to a three-liter, three-necked flask fitted with a stirrer, condenser and pressure equalized, closed addition funnel. The addition funnel is also fitted with a connection to a source `of nitrogen so that nitrogen can be used to purge and F 19 sweep the flask contents. Over a two-hour period a solution of 150 milliliters of acetone, 400 milliliters methanol and 150 milliliters concentrated hydrochloric acid are introduced into the flask to convert the reactive byproducts to hydrogen and borates. The flask contents are stirred for an additional l2 hours until no more gas is evolved and the resultant solution is then placed in a one-liter addition funnel and added slowly to three gallons of water maintained at a temperature of 95 o*100 C. Some decomposition of additional byproducts occurs; the hydrochloric acid and acetone are extracted into the water phase and the benzene is vaporized from the system. The aqueous mixture is stirred for an additional 10 minutes and the crude carborane which separates as a solid in the aqueous phase is removed and dissolved in 500 milliliters methanol in a two-liter Erlenmeyer flask.

The crude carborane is then purified by the addition of a solution of 50 grams potassium hydroxide in 75 milliliters of Water and agitated for 3 minutes, then poured into 3 gallons of ice water, stirred for 10 minutes, and filtered. The filtered solid is then dried in a vacuum over phosphorus pentoxide and the dried product is mixed with 30 grams anhydrous calcium chloride and placed in thimble of a Soxhlet extraction apparatus. The mixture is extracted with 500 milliliters of heptane for 20 hours. The carborane is recovered from the heptane by crystallization and filtration by placing the heptane in a rotary evaporator heated with a steam bath to evaporate the heptane to 50 milliliters. After separation of the carborane, the filtrate is cooled and a second crop of carborane is obtained. The combined yield after drying is about 85 grams and an additional 3 to 4 grams of impure material may be obtained by evaporating the hexane solution to dryness. In repeated runs this impure material can be added to the mixture in the Soxhlet thimble for further purification.

Example Z-Preparation of bromomethylcarborane The following illustrates the preparation of l-bromomethyl-1,2-dicarbaclovodecaborane(12). A three-necked flask and the apparatus described in the previous experiment is employed in the preparation of the bromomethylcarborane. The reaction flask is purged and filled with nitrogen, then charged with 49.9 grams deeaborane, 32 milliliters acetonitrile, 35 milliliters propargyl bromide and 350 milliliters of benzene. The solution is stirred and heated at reflux temperature for two hours and thereafter the introduction of the propargyl bromide is initiated by introduction of 11 milliliters of the propargyl bromide through a nitrogen-filled addition funnel dropwise over a one-hour period. The addition funnel is then removed, the flask stoppered and the solution is maintained at reflux temperature for 11/2 hours and then the flask is unstoppered, the addition funnel is replaced, and an additional quantity of 11 milliliters propargyl bromide is introduced. After 11/2 hours of stirring of the flask contents at reflux temperature, the remainder of the propargyl bromide is introduced and the flask contents are again stirred for 11/2 hours at reflux temperature.

The solution is then cooled to room temperature and washed with 4benzene into a single necked flask. The solvent is removed from the flask using -a water aspirator vacuum and gentle heating from a steam bath. The residue in the flask is then cooled to room temperature, removed from the vacuum and 200 milliliters of hexane is added and stirred with `the residue to extract most of the carborane. The hexane extract is decanted and the brownish tar is again extracted with 40 milliliters of hexane. The second extraction converts the tar residue to a solid which is removed by filtration and washed on the filter with an additional 40 milliliters of hexane. The combined hexane extracts are filtered and washed in a separatory funnel with four 100 milliliter portions of chilled aqueous l weight percent sodium hydroxide solution and then with four 100 milliliter portions of water.

The hexane solution, yellow in color, is dried over anhydrous magnesium sulfate and filtered and the solvent is then evaporated in a rotary evaporator using a water aspirator.

The carborane remaining in the evaporator flask is washed with a small amount of pentane into a single necked 300 milliliter flask which is attached to an alembic column. Glass wool is placed in the solution, in the neck of the alembic distillation column, and at the stop of the column to inhibit bumping during the distillation. The distilling llask, collecting flask and column are continuously evacuated with a high vacuum system. When the bulk of the pentane and residual hexane have distilled away, the temperature of the water bath surrounding the distillation flask is raised from room temperature to 125 C. over a one-hour period. When the distillation rate slows appreciably, the flask contents are raised to 150 C. and maintained -there until no more distillate is obtained. The distillation flask is then cooled to room temperature, the vacuum is reduced on the system, and the product is removed to recover 86.5 grams of distilled product. The bromornethylcarborane may be further purified by crystallization from pentane or methanol if desired.

Example 3-Methylcarborane The following describes the preparation of 1-methyl- 1,Z-dicarbaclovodecaborane(12). This material is prepared by hydrolysis of the Grignard reagent formed from the reaction of bromomethylcarborane; see the preceding preparation; with magnesium in the presence of diethylether. The preparation is carried out in a one-liter, 3- necked flask equipped with a mechanical stirrer, reflux condenser, pressured equalized, closed addition funnel and nitrogen inlet. The flask is maintained filled with nitrogen throughout the `course of reaction. The flask is charged with 6.1 grams magnesium chips, 50 milliliters of anhydrous diethylether, warmed to 30 C., and then a solution of 50 grams of distilled bromomethylcarborane dissolved in 300 milliliters of anhydrous diethylether is introduced slowly into the flask While the flask contents are stirred. The flask is gently warmed to reflux temperature and then the heating mantle is removed and the addition of the carborane solution is maintained at a rate suflcient to maintain the reflux temperature. The bromoethylcarborane solution is added within about 35 minutes and the stirred reaction mixture is then maintained at reflux temperature by heating for 21/2 hours.

The solution is then cooled to room temperature and is decanted from the excess magnesium into a 2-liter beaker half-filled with crushed ice. The carboranyl magnesium bromide is washed into the ice mixture with two 50 milliliter portions of diethylether. Hydrochloric acid of 3 normality in a sufficient quantity to dissolve the magnesium salts is added to the stirred ice mixture and the ether and water layers are separated. The water layer is extracted three times with milliliter portions of diethylether. After the combined ether extracts are dried over anhydrous magnesium sulfate, the ether is removed in a rotary evaporator. The evaporator flask contents are then dissolved in milliliters of hot methanol and the solution is permitted to cool slowly to 0 C. The methyl carborane crystallizes from the methanol and is filtered therefrom. A portion of the methanol liquor is removed, heated and water added to the solution until it becomes cloudy. The solution is then cooled to 0 C. to obtain an addition crop of methyl carborane crystals. The combined crops are dried in a vacuum to yield 3l grams of methyl carborane.

l,2-dimethyl-l,2 dicarbaclovodecaborane(l2) is prepared by the hydrolysis of the Grignard reagent formed from the reaction of bromomethylcarborane with magnesium in the presence of tetrahydrofuran.

A one-liter, three-necked ask equipped with a mechanical stirrer, reflux condenser, addition funnel and nitrogen inlet is thoroughly dried and flushed with nitrogen. Into the ask is placed 6.1 grams of clean magnesium chips and about 15 milliliters of tetrahydrofuran. The closed addition funnel is charged With 50 grams of distilled bromomethylcarborane dissolved in 250 milliliters of tetrahydrofuran. About 50 milliliters of `the solution is then rapidly added to the stirred magnesium suspension to cause initiation of the Grignard reaction. The rate of addition is controlled thereafter so that the heat of the reaction is sucient to maintain reflux temperature. After addition is complete, the flask is maintained at reflux temperature for an additional 2.5 hours.

The cooled reaction solution is rapidly decanted under nitrogen from the excess magnesium into a second oneliter, three-necked flask equipped with a mechanical stirrer, addition funnel, Dry Ice condenser and nitrogen inlet. The addition funnel of this flask is charged with 48 grams of methyl iodide and the methyl iodide is then added dropwise to the solution in the flask at an addition rate to maintain a reux temperature. Upon completion of the addition of methyl iodide, the solution is maintained at the reflux temperature for an additional 3 hours and then cooled. The cooled mixture is then slowly added to about 400 milliliters of chilled dilute l N hydrochloric acid. The product is extracted with 250 milliliters of diethylether and then with 375 milliliter portions of diethylether. The combined ether extracts Ifrom the aqueous phase are Washed once with 75 milliliters of Water and then dried over magnesium sulfate. The diethylether solvent is then evaporated under vacuum using a rotary evaporator and the flask contents are then dissolved in ethanol. The product is separated from the ethanol by crystallization by cooling the ethanol and additional crops of crystals are obtained from the mother liquor by concentrating the mother liquor and adding Water to the solution until it becomes cloudy and then cooling the solution to C. The total of 33 grams of product is crystallized from the ethanol liquor.

Example -Phenylcarborane l-phenyl 1,2 dicarbaclovododecaborane(12) is prepared from decaborane, acetonitrile and phenylacetylene following a procedure similar to that set forth in Experiment 2 for the preparation of bromomethylcarborane. The reaction flask is charged with 50 grams purified decaborane, 22 milliliters acetonitrile and 500 milliliters benzene. The solution is refluxed for two hours and thereafter the 42 grams of phenylacetylene is added dropwise and the mixture is then reuxed for hours. The solvent is removed under vacuum in a rotary evaporator, the residue is extracted with 1 milliliter pentane and the pentane solution is Washed 4 times with 100 milliliter portions of l()` weight percent sodium hydroxide solution. The pentane solution is then dried over anhydrous magnesium sulfate and the solvent is removed with a rotary evaporator at reduced pressures to give 61.5 grams of crystalline phenylcarborane.

Example G--Phenylcarborane isomerization 1 phenyl 1,7 dicarbaclovodecaborane(12) is prepared by thermal rearrangement of the phenylcarborane prepared in the preceding experiment. This thermal rearrangement is performed in a 100` milliliter stainless steel autoclave which is charged With 5 grams of the phenylcarborane of the preceding example. The autoclave is evacuated with a mechanical vacuum pump and then heated electrically to a temperature of 420 C. for 24 hours. After cooling, the contents of the autoclave are dissolved in 30 milliliters of pentane and analyzed by thin layer chromatography to obtain 3.4 grams of the l-phenyl- 1,7-dicarbaclovodecaborane and 1.5 grams of the unconverted 1-phenyl-1,2carborane.

An ammonium monocarborane is prepared by the reaction of decaborane(14) with an isocyanide. The decaborane is charged to the reaction flask in benzene and ethyl isocyanide is added at room temperature. After one hour at room temperature, the flask contents are filtered, the separated solid is dried and dissolved in hot water. The aqueous extract is then cooled to yield about 70 percent of an ammonium monocarborate,

CzHfsNHzCBluHm Example 8-C-ammonylmonocarborane In another preparation, decaborane( 14) is reacted with sodium cyanide by the addition of 0.28 gram of decaborane to a solution of 0.35 gram sodium cyanide in 200 milliliters water. The solution is stirred for 5 hours at 25 C. and then passed over a hydrogen charged ion exchange solid (Amberlite IR-l20). The efuent comprises an aqueous solution of C-ammonylmonocarborane.

Example 9-Dimethyl derivatives The following experiments describe the preparation of (3 -1,2-dicarbadodecahydroundecaborates:

The 1,2 dimethyl-(3)-l,2-dica'rbadodecahydroundecaborate(-1); [B9C2H10(CH3)2]1 is prepared by the treatment of dimethylcarborane with alcoholic base to abstract a boron atom from the carborane. This reaction is performed in a 500 milliliter, three-necked ask equipped with a reflux condenser, a mechanical stirrer and a nitrogen inlet. To the llask is charged a solution of 2O grams potassium hydroxide in 300 milliliters of absolute ethyl alcohol. The solution is cooled to room temperature and then 30 grams of dimethylcarborane is added and the solution is stirred for one hour at room temperature and then heated to reflux temperature and maintained at that temperature until the evolution of hydrogen has ceased. The flask contents are then cooled and an additional 10() milliliters of absolute ethyl alcohol is added and carbon dioxide is then introduced into the solution to precipitate excess potassium hydroxide as the carbonate. The precipitate is removed by iiltration and Washed :five times with 50 milliliter portions of absolute ethyl alcohol. The combined filtrate and Washings are evaporated to dryness to yield a crude potassium salt which is Water soluble and which can be base-exchanged with other cations such as trimethyl ammonium, cesium, etc.

Other dicarbadodecahydroundecaborate derivatives The (3) 1,2 dicarbadodecahydroundecaborate(-1) ion, the 1 phenyl-(3)-1,2-dicarbadodeoahydroundecaborate( ion, and the (3)-1,7-dicarbadodecahydroundecaborate( 1) ion are prepared in the same manner with the exception that the 1,7-isomer is formed under higher temperature conditions than the corresponding 1,2-isomers. This is accomplished by carrying out the initial alcoholic potassium hydroxide degradation in a stirred autoclave under pressure at about 150 C.

Example l-Dicarbollide preparation The dicarbollide ions were prepared from the products of the preceding example by treatment to abstract a proton from the face of the dicarbadodecahydroundecaborate ions described in the preceding examples. The tirst preparation uses an alkali metal in a solvent while the second method utilizes highly concentrated aqueous alkali metal hydroxide.

Anhydrous dicarbollide preparation In this preparation a 500 milliliter, three-necked flask fitted with a mechanical stirrer, nitrogen inlet and reuX condenser is charged with milliliters tetrahydrofuran and 6.1 grams of sodium metal dispersed in a mineral oil. The mixture is stirred and then 17.3 grams of potassium dicarbadodecahydroundecaborate is added under a stream of nitrogen. The flask is heated to reflux temperature and hydrogen is rapidly evolved. The solution is maintained at reflux temperature for 20 hours and the excess sodium is removed. The precipitate in the cooled flask is then recovered by filtration and this comprises the disdium( 1 )2,3dicarbollide (NazBgCZHu). This material can be purified by extraction in a Soxlet apparatus with 500 milliliters of sodium dried 4benzene while main tained under a nitrogen atmosphere for 48 hours. The unextracted residue comprises 3.2 grams and is recovered and dried.

Alternative anhydrous carbollide preparation An alternate method for carbollide preparation comprises charging 1.51 grams sodium hydride in 90 milliliters tetrahydrofuran tothe 500Y milliliter three-necked reaction ask and adding thereto 5 grams of the trimethylammonium dicarbadodecahydroundecaborate dissolved in 75 milliliters of tetrahydrofuran. The reaction mixture is stirred at reflux temperature under nitrogen for 3 hours or until no more gas is evolved. After completion of the reaction, the stirring is ceased and excess sodium hydride is permitted to settle and the solution is decanted and is suitable for use if promptly reacted with a metal salt or metal complex to form the dicarbollyl metal complex; see Example 4.

Example l1 The following example will illustrate the prepara-tion of carboranes having ligand substituents on face boron atoms. These carboranes can be treated in the same manner as set forth in Example to prepare dicarbollide anions which can then be reacted as indicated in Example 12 in the preparation of carbollyl metal complexes.

B-tetrahydrofuran derivatives The B tetrahydrofuran substituted dicarborane (BBCzHuBTHF) and its C-phenyl and C,C'dimethy1 derivatives are prepared by an oxidative substitution reaction. The preparation is performed in the three-necked, two-liter flask previously described, having a mechanical stirrer, pressure equalized addition funnel and a l2-inch distillation column with a take-off head and reflux condenser. An inlet is provided to allow nitrogen to be introduced under the liquid level through a medium porosity tted glass dispersion tube. To the flask is added (under a stream of nitrogen), 500 milliliters of benzene which has previously been dried over sodium ribbon, milliliters of freshly distilled tetrahydrofuran and `8.6 grams of benzene extracted potassium dicarbadodecahydroundecarborate.

A solution of anhydrous ferric chloride in tetrahydrofuran is prepared in a 500 milliliter Erlenmeyer flask equipped `with a magnetic stirrer by introducing (under a stream of nitrogen), 200 milliliters of sodium dried benzene and 40 `milliliters of freshly distilled tetrahydrofuran and then adding thereto with stirring 16.2 `grams of sublimed anhydrous ferric chloride.

The resultant deep red solution is transferred to the addition funnel of the two-liter flask under a stream of nitrogen. The stirred solution in the 2-liter flask is then heated to reflux temperature and the ferric chloride solution is added dropwise from the pressure equalized addition funnel over a period of one hour. As the ferric chloride solution contacts the reuxing solution in the flask, the ferric chloride is decolorized, hydrogen chloride is evolved and a solid precipitate is formed. The hydrogen chloride is removed from the mixture by sweeping nitrogen through the solution and after the ferric chloride solution has been added to the 2-liter flask, the excess tetrahydrofuran is distilled overhead through the distillation column at a reflux ratio of about 10:1. The distillation is continued until the boiling point of the overhead distillate is that of benzene (80) and then the reaction `mixture is cooled to room temperature and filtered through a Buchner funnel.

The solid precipitate on the funnel is washed with hot benzene, the filtrate and washings are combined, placed in a separatory funnel and washed with 200 milliliter portions of distilled water until the aqueous phase is neutral .to pH paper, The benzene solution is then dried over anhydrous magnesium sulfate and evaporated under vacuum to approximately 200 milliliters volume using a rotary evaporator. During the evaporation the flask contents are warmed to about 50 C. with a water bath. Approximately milliliters of heptane are then added to the flask contents and the resultant solution is chilled in a methanol ice bath to recover a product by crystallization comprising 6.1 grams. Further concentration and crystallization of the mother liquor yields an additional YV4V grarns-ofW product.Y The product is a mixture of nsymr a metrica! and asymmetrical BQCZHHTHF.

Using the same procedure, 13 grams of gave 13.4 grams of B9C2H10(C6H5)THF. Similarly, 15 grams of CSB9C2H10(CH3)2 reacted to give 11.2 grams of the mixed isomers of B9C2H9(CH3)2THF.

B-pyridine derivatives The procedure of Experiment 11 is repeated, substituting pyridine for tetrahydrofuran previously employed and reacting 10 grams of (CH3)3NHB9C2H12 to Obtain 10.8 grams of B9C2H11PY. Using the same procedure substituting pyridine for the tetrahydrofuran and 15 grams of CSB9C2H10(CH3)2 iyelds grams 0f The C-phenyl derivative is prepared by the reaction of 13 grams of (CH3)3NHB9C2H11(C6H5) with pyridine in the presence of ferric chloride. Following the procedures set forth above 13.8 grams of B9C2H10(C6H5)PY is obtained.

B-acetonitrile derivatives The substitution of acetonitrile for the tetrahydrofuran in the general procedure described in Experiment 11 reysults in the preparation of a boron-substituted acetonitrile derivative. Excess acetonitrile from the reaction is distilled from the reaction mixture as a 34 percent acetonitrile benzene azeotrope which boils at 73 C. The reaction is performed by charging 13 grams of the cesium salt of the dicarbadodecahydroundecarborate to the reaction flask and reacting it with acetronitrile in the presence of ferric chloride to produce 8.4 grams of the acetonitrile derivative, B9C2H11CH3CN.

The procedure is repeated charging 15 grams of the cesium salt of the 1,Z-dimethyl,1,2-dicarbadodecahydroundecaborate to the reaction flask and reacting this material with acetonitrile in the presence of ferric chloride to produce 10.1 grams of the acetonitrile dimethyl derivative having the following formula:

In a similar fashion, acetonitrile is reacted in the presence of ferric chloride with 12 grams of the potassium salt of C-phenyl dicarbadodecahydroundecaborate to produce 10.9 grams of the acetonitrile derivative having the following formula:

B9C2H10 (C6H5) CHaCN Diethyl sulde derivatives The diethyl sulde derivatives of the dimethyl dicarbadodecahydroundecaborate is prepared by charging 15 grams of cesium dicarbadodecahydroundecarborate to the reaction flask and reacting this tmaterial with diethylsulfide in the presence of ferric chloride. The excess diethylsulde is separated from a benzene solution of the crude reaction products by chromatographic separation. This is achieved by dissolving a crude product in benzene and applying the solution to a chromatograph column one inch in diameter by four feet in length and eluting the solution with a mixture of 60 percent benzene and 40 percent pentane. The excess diethylsulde is removed in the solvent front and discarded. The remainder of the column effluent is evaporated to dryness to yield 11.4 grams of the solid diethylsulde derivative, B9C2H9(CH3)2S(C3H5)2. This material comprised a lmixture of the asymmetric and symmetric isomers.

Triphenylphosphine derivatives The triphenylphosphine substituted borane and its C, Cdimethyl derivative is prepared by charging 11 grams of the trimethyl ammonium salt of dicarbadodecahydroundecaborate to the reaction flask together with 500 milliliters benzene, and 26 grams of triphenyl phosphine. The pressure equalized addition funnel is equipped with a 2 milliliter glass tube which extends to just above the stopcock in the addition funnel. A slurry of ferrie chloride in benzene is placed in the addition funnel and maintained in a uidized condition by bubbling a stream of nitrogen through this 2 milliliter dip tube. The remainder of the reaction is carried out according to the procedure described in the preparation of the tetrahydrofuran derivatives. After completion of the reaction the crude product is filtered, washed and dried and evaporated to dryness to give a solid residue. The residue is placed in a soxhlet extractor and extracted with 250 milliliters of heptane for about 2 hours under nitrogen to remove excess triphenyl phosphine. Upon completion of the extraction, the unextracted residue is re-crystallized from a benzene-heptane mixture to give 15.2 grams of the triphenyl phosphine derivative B9C2H11P(C6H5)3. This material is analyzed and found to comprise a mixture of the symmetric and asymmetric isomers.

The same procedure is repeated charging 15 grams of the cesium salt of the l,2-dimethyl-1,2-dicarbadodecahydroundecaborate `with 52.4 grams of triphenyl phosphine in the presence of ferrie chloride to give 10.2 grams of crystalline B9C2H9(CH3)2P (C6H5)3 which is a mixture of the symmetric and asymmetric isomers.

Ethoxy derivative The B-alkoxy derivative is prepared by performing a ligand exchange reaction with the tetrahydrofuran ligand derivative previously prepared. This reaction is performed by charging the symmetrical isomer of B9C2H9(CH3)2 tetrahydrofuran to potassium hydroxide in ethanol and heating the resulting solution for a few minutes and then diluting it with an equal volume of water. To the reaction flask is then added tetramethylammonium chloride and the alcohol Iwas allowed to evaporate slowly at room temperature. As the alcohol evaporated, crystals of the trimethylarnmonium salt of the monovalent anion precipitate. This ligand derivative is the symmetrical derivative indicating that no isomerizaton occurs during the ligand exchange.

Example 12 The carbollyl metal complexes are prepared by the reaction of the carbollide anions described in Example 2 with metal salts or ligand metal complexes. A- typical preparation comprises the addition of a tetrahydrofuran solution of the alkali metal salt of the carbollide ion to an anhydrous solution of the metal salt in tetrahydrofuran.

Iron complexes The iron(II) complex is prepared from a solution of ferrous chloride which is obtained by placing 1.5 grams of iron powder, 100 mesh, 6 grams of anhydrous sublimed ferric chloride and 150 milliliters of tetrahydrofuran in a reaction ask stirring the mixture until the iron powder has dissolved as ferrous chloride. The sodium salt of the dicarbollide anion is prepared simultaneously under nitrogen in a 300 milliliter, three-necked, roundbottom ask equipped with a condenser, addition funnel and magnetic stirring rod. To the llask is charged 1.51 grams sodium hydride in milliliters tetrahydrofuran. A solution of 5 grams of the trimethyl ammonium salt of the monovalent dicarbadodecahydroundecaborate anion dissolved in 75 milliliters tetrahydrofuran is placed in the addition funnel and slowly added to the sodium hydride solution. The reaction mixture is stirred at reflux temperature until no more gas is evolved, approximately 3 hours. The solution is permitted to cool to room temperature and after the excess sodium hydride has settled, the tetrahydrofuran solution of the disodium dicarbollide anion is decanted into the ferrous chloride tetrahydrofuran mixture under a ow of nitrogen. The resultant mixture becomes dark red and this mixture is stirred for one hour at room temperature under nitrogen. The reaction solution is thereafter decanted into a 500 milliliter round-bottom flask and the solvent is removed at ambient temperature using a rotary evaporator and mechanical pump vacuum. Prior to distillation the solution is stirred for 45 minutes in the presence of air to change the oxidation state of the iron from (II) to (III) corresponding to the following change:

The residue in the evaporation ask is dissolved in 250 milliliters of water, ltered through diatomaceous earth, and the ltrate is placed in a separatory funnel and Washed with two milliliter portions of pentane. The aqueous layer is again filtered through the diatomaceous earth and the tetramethyl ammonium salt of the bis-1rdicarbollyl iron(III) is precipitated from the filtrate by the addition of 20 milliliters of 50 percent aqueous tetramethyl ammonium chloride. The precipitate is collected by filtration, washed three times `with 300 milliliter portions of water and then placed in a 500 milliliter roundbottom ask in a mixture of 200 milliliters acetone and 80 milliliters water. The solvent is evaporated using a rotary evaporator and water aspirator vacuum and the product crystallizes from the solution. The 'first crop of crystals yields about 3.12 grams and successive crops of crystals are obtained by further removal of the solvent. Total yield of crude product is 3.72 grams and further purification can be accomplished by repeated recrystallization from acetone-water and acetone-hexane extracts. This procedure is repeated with the 1,2-dimethy1 dicarbollide anion and with the l-phenyl dicarbollide anion to plrepare the corresponding bis-n-dicarbollyl iron comp exes.

A carbonylcarbollyl metal complex is prepared by introducing 150 milliliters of a tetrahydrofuran solution of 0.023 mole of disodium(1)-2,3dicarbo1lide into a quartz glass cylinder. An equal molar quantity (8.1 grams) of tungsten hexacarbonyl is then added and the tube is ushed and blanketed with nitrogen and then irradiated with ultraviolet light for about 40` hours until gas evolution ceases. The liquid contents of the cylinder are poured into 2 liters of water and an aqueous solution of tetramethylammonium chloride is added to precipitate about 10 grams of the salt, tetramethylammonium tricarbonyldicarbollyltungstate.

Example l3-Monocarbollide iron complex A bis-1r-(1)2monocarbollyl iron complex is prepared by charging the ethyl ammonium monocarborate to a 250 milliliter round-bottom flask and adding thereto 75 milliliters of 50 percent aqueous sodium hydroxide. To the reactants is then charged a ferrous chloride aqueous solution containing 9.41 grams of ferrous chloride in 25 milliliters water. The mixture is heated to 70 C. on a steam bath while maintained under a nitrogen atmosphere. Ferrous hydroxide immediately precipitates and the reaction solution is periodically agitated for 30 minutes. Upon completion of the reaction the solution is diluted 27 with 200 milliliters of water and filtered through a center disc filter containing a layer of diatomaceous earth. The residue in the lter funnel is washed three times with 20 milliliters of hot water and the filtrate and washings are acidied with 6 N hydrochloric acid to a pH of 4. The solution is permitted to oxidize to the ferric (III) state by the addition of a trace amount of ferrie chloride hexahydrate and introduction of air into the solution. The solution is then brought to a pH of 8 with aqueous sodium hydroxide and the ferrie hydroxide is removed by filtral tion. The aqueous solution is then mixed with milliliters of percent aqueous tetraethylammonium chloride to precipitate the tetramethylammonium salt of the bis-1rmonocarbollyl iron(III), (CH3)4N[(1r-B10CH11)2F6].

A nickel complex is prepared by dissolving 11 grams of 15 C-ammonylmonocarbollide in milliliters of a 16 weight percent sodium hydroxide solution. To the resultant solution is added 75 milliliters of an aqeous solution containing 22 grams of nickel chloride. The resultant solution is heated on a steam bath for about 30 minutes and then 20 ltered. To the filtrate is added a solution of cesium chloride, the admixture is cooled and the cesium salt, dicesium bis (C-amrnonylmonocarbollyl) nickelate (IV) is crystallized from the mixture. A neutral complex is obtained by dissolving this cesium salt in hot Water and passing the 25 solution through a column containing a strong acid ion exchange resin, Rexyn 101 (H). The column eiuent is collected and dried to obtain the bismonoearbollylnickel(IV) complex.

EXAMPLE 14 30 The following illustrate motor fuel compositions of my invention:

Gasoline 1 Gravity API at 60 F.57-60 35 Boiling range, F.-85405 Vapor pressure-9.0-14 p.s.i. at 100 F. Bis-dicarbollyl nickel(IV)-0.03 weight percent Surfactant (fatty amine)-0.001 weight percent Phenolic gum inhibitor-10 pounds/ 1000 barrels 40 Parainic lubricating oil-0.6 lweight percent Sulfur- 0.04 weight percent Gasoline 2 Gravity oAl-"I at F.-58 Boiling range, F.-92-425 45 Vapor pressure-9.0-11-0 p.s.i. at 100 F. Cyclopentadienyldicarbollyl iron(III)-0.001 Weight percent Surfactant (fatty amine)-0.002 weight percent Sulfur- 0.04 weight percent 50 Gasoline 3 Gravity API at 60 F.-62 Boiling range, F.-90-380 Sulfur-0.01 Hexa(dirnethylsulfoxo)monocarbollylaluminum(111)- 55 0.01 weight percent Gasoline 4 Gravity API at 60 F.-64.0 Boiling range, F.-115-580 60 Lubricating oil-4.5 Weight percent Sulfur- 0.01 weight percent Vapor pressure p.s.i. at 100 F.-5 Tricarbonyldicarbollyltungsten-O.5 weight percent AVIATION GAsoLrNns Grade 80/87 10o/130 115/145 Gravity API at 60 F 67. 6 71. 2 68. 4 Distillation F.; percent evaporation:

233 241 252 0, 01 0.10 o. 01 Vapor pressure 6. 9 6. 8 6.9 Weight percent of complex:

Triearbonyldicarbollylmanganesc (1r) 0.20 Bisdiearb ollylchromium (IV) 0. 06 BidicarboHyltnGV) 0.10

28 The following illustrates compression ignition motor fuel compositions of my invention:

Diesel 1 Gravity API-28.7 Flash point PMCC-170 F. Viscosity SSU at F.-49 Cyclopentadienyldicarbollyliron(HD-1.0 weight percent Diesel 5 Gravity API-38-43 iFlash point PMCC F.-135150 Viscosity SSU at 100 F.-31-32 Monocarbollyldicarbollylvanadium(V)0.001 weight percent Diesel `6 Gravity API-39-40 Viscosity SSU at 100 F.-3334 Bis(B-ethoxydicarbollyl) zinc(II)-l.5 weight percent Diesel 7 Gravity API-45,2

Flash point PMCC F .-130

Viscosity SSU at 100 =F .-31.9 Bisdicarbollyltin(IV)-2.0 weight percent Example 15 The following will illustrate various burner fuel coinpositions of my invention:

Fuel oil 1 Gravity API-1.06.0 Flash point PMCC F.180-250 Viscosity SSF at 122 F.-170 Tricarbonyldicarbollylmanganese (ID- 0.01 weight percent Fuel oil 2 Gravity API- 7040.0

Flash point PMCC F.-170-180 Viscosity SSF at 122 F.-80-ll0 Bisdicarbollylmolybdenum(1V )-0.005 weight percent Fuel oil 3 Gravity API-11.0-14.5

Viscosity SSU at 100 F .-170-850 Tricarbonyldicarbollylrhenium(Il)-0.05 weight percent Fuel oil 4 Gravity API-33-34 Viscosity SSU at 100 F.-3638 Tricarbonylmonocarbollyliron (HD- 0.1 weight percent Kerosene fuel Gravity API-43 Viscosity cs. at 100 F.-1.8

Bisdicarbollylchromium (IV)-1.5 Weight percent Example 16 The following will illustrate jet fuels of my invention:

Jet fuel 1 (JP-4) Gravity API at 60 F14-55 Boiling range, 10-90 percent-208-4l4 Aromatics-23 volume percent Olens-3 volume percent Sulfur-0.15 weight percent Carbonylmonocarbollylcopper(HD-0.01 weight percent Jet fuel 2 (IP-5/6) Boiling range, 10-90 percent-350-465 F. Aromatics-17 volume percent Sulfur0.2 weight percent Bisdicarbollylnickel(IV) 1.2 weight percent Example 17 The anti-knock properties of the carbollyl metal complex was determined by the addition of the carbollyl metal complex to unleaded base gasoline stock and tested in standard anti-knock test engines. The gasoline stock had the following properties:

Distillation 10-90% overhead--l43-300 Gravity API-52.9 Vapor pressure--7.85

The aforementioned base stock had a motor octane number of 86.8 and a research octane number of 97.8. To separate quantities of the aforementioned base gasoline stock were added sufficient amounts of two carbollyl metal complexes to provide concentrations of 0.1 and 1.0 gram of the complex per gallon. The following carbollyl metal complexes were employed:

( 1) Cyclopentadienyldicarbollyliron(III) I1FC5H5FCB9C2H11I (2) Bis-n-dicarbollylnickel(IV) [1r-(B9C2H11)2Ni] The resulting blends were tested for octane numbers using the motor and research octane method and the following results were obtained:

INCREASES IN OCTANE NUMBERS Iron complex Nickel complex Concentration of carbollyl metal complex Motor Research Motor Research 0.1 gram/gallon 0. 10 0. 26 0. 13 0. 36 1.0 gram/gallon 0. 30 0. 76 0. 38 0. 75

In addition to the increase in octane number set forth in the preceding table, the additive effect was observed to have a prolonged residual effect on the operation of the engines in that it was necessary to operate the engines for approximately 30 minutes on the base fuel containing no additive after the addition of the additive containing fuel to remove the increased octane number result.

I claim:

1. A liquid hydrocarbon motor fuel comprising a major proportion of a liquid hydrocarbon fuel and a minor amount of a complex between a metal having orbitals of 1r-syrnmetry and capable of contributing at least one electron to bonding in the complex and a carbollide having the following formula:

wherein:

X is hydride or halide;

R is alkyl, aryl, alkenyl or haloalkyl having from 1 to about l2 carbons; R' is hydride, halide, ammonium, alkyl, aryl, alkenyl, carboxyl, carboxyethyl or cycloalkyl having from 1 to about 12 carbons; and

Y is a ligand which is an unsaturated aliphatic or alicyclic hydrocarbon having from 2 to about 15 carbons or which has at least one atom that is halogen, oxygen, nitrogen, sulfur or trivalent phosphorus, bismuth, arsenic or antimony;

o is 1 or 2;

n is 0, 1 or 2;

pis 0 or l; and

2. The liquid motor fuel of claim 1 wherein said complex has a zero net charge.

3. The liquid motor fuel of claim 1 wherein said metal is a Group VIII metal.

4. The liquid motor fuel of claim 1 wherein said carbollide is a dicarbaundecahydroundecaborate anion.

5. The liquid motor fuel of claim 2 wherein said carbollide is a monocarbaundecahydroundecaborate anion.

6. The motor fuel of claim 1 wherein said fuel is for an internal combustion engine and said complex is a nickel carbollyl complex in sufficient concentration to increase the octane rating of the fuel.

7. A liquid hydrocarbon motor fuel comprising a major proportion of a liquid hydrocarbon fuel and a minor amount of a complex between a metal having orbitals of -lr-symmetry and capable of contributing at least one electron to bonding in the complex and a carbollide having the following formula:

3 wherein:

X is hydride or halide; 'R is alkyl, aryl, alkenyl or haloalkyl having from 1 t0 about 12 carbons; R' is hydride, halide, ammonium, alkyl, aryl, alkenyl, carboxyl, carboxyethyl or cycloalkyl having from 1 to about 12 carbons; and Y is a ligand which is an unsaturated aliphatic or alicyclic hydrocarbon having from 2 to about l5 carbons or which has at least one atom that is halogen, oxygen, nitrogen, sulfur or trivalent phosphorus, bismuth, arsenic or antimony; ois 1 or 2; nis 0, 1 or 2; p is 0 or 1; and mis ll-(o-l-n-l-p). 8. The motor fuel of claim 1 wherein said liquid hydrocarbon fuel is gasoline.

9. The motor fuel of claim 7 wherein said liquid hydrocarbon fuel is gasoline.

References Cited UNITED STATES PATENTS 3,320,165 5/1967 Bridger et al 44-63 3,420,889 1/1969 Onak 260-606.5B 3,437,596 4/ 1969 McCabe 44-63 3,446,808 5/ 1969 Cyba 44-63 OTHER REFERENCES Journal Amer. Chem. Soc., vol. 87, p. 1818, Apr. 20, 1965.

Journal Amer. Chem. Soc., vol.. 90, pp. 879-895, Feb. 14, 1968.

DANIEL E. WYMAN, Primary Examiner Y. H. SMITH, Assistant Examiner U.S. Cl. XR. 

